Jianzhi Xu, Ya-Ke Li, Ewald Janssens and Gao-Lei Hou,
{"title":"富勒烯-金属团簇的多包层:从基础到应用","authors":"Jianzhi Xu, Ya-Ke Li, Ewald Janssens and Gao-Lei Hou, ","doi":"10.1021/acs.accounts.4c00130","DOIUrl":null,"url":null,"abstract":"<p >Buckminsterfullerene, C<sub>60</sub>, was discovered through a prominent mass peak containing 60 atoms produced from laser vaporization of graphite, driven by Kroto’s interest in understanding the formation mechanisms of carbon-containing molecules in space. Inspired by the geodesic dome-shaped architecture designed by Richard Buckminster Fuller, after whom the particle was named, C<sub>60</sub> was found to have a football-shaped structure comprising 20 hexagons and 12 pentagons. It sparked worldwide interest in understanding this new carbon allotrope, resulting in the awarding of the Noble Prize in Chemistry to Smalley, Kroto, and Curl in 1996.</p><p >Intrinsically, C<sub>60</sub> is an exceptional species because of its high stability and electron-accepting ability and its structural tunability by decorating or substituting either on its exterior surface or interior hollow cavity. For example, metal-decorated fullerene complexes have found important applications ranging from superconductivity, nanoscale electronic devices, and organic photovoltaic cells to catalysis and biomedicine. Compared to the large body of studies on atoms and molecules encapsulated by C<sub>60</sub>, studies on the exteriorly modified fullerenes, i.e., exohedral fullerenes, are scarcer. Surprisingly, to date, uncertainty exists about a fundamental question: what is the preferable exterior binding site of different kinds of single atoms on the C<sub>60</sub> surface?</p><p >In recent years, we have developed an experimental protocol to synthesize the desired fullerene–metal clusters and to record their infrared spectra via messenger-tagged infrared multiple photon dissociation spectroscopy. With complementary quantum chemical calculations and molecular dynamics simulations, we determined that the most probable binding site of a metal, specifically a vanadium cation, on C<sub>60</sub> is above a pentagonal center in an η<sup>5</sup> fashion. We explored the bonding nature between C<sub>60</sub> and V<sup>+</sup> and revealed that the high thermal stability of this cluster originates from large orbital and electrostatic interactions. Through comparing the measured infrared spectra of [C<sub>60</sub>-Metal]<sup>+</sup> with the observational Spitzer data of several fullerene-rich planetary nebulae, we proposed that the complexes formed by fullerene and cosmically abundant metals, for example, iron, are promising carriers of astronomical unidentified spectroscopic features. This opens the door for a real consideration of Kroto’s 30-year-old hypothesis that complexes involving cosmically abundant elements and C<sub>60</sub> exhibit strong charge-transfer bands, similar to those of certain unidentified astrophysical spectroscopic features. We compiled a VibFullerene database and extracted a set of vibrational frequencies and intensities for fullerene derivatives to facilitate their potential detection by the James Webb Space Telescope. In addition, we showed that upon infrared irradiation C<sub>60</sub>V<sup>+</sup> can efficiently catalyze water splitting to generate H<sub>2</sub>. This finding is attributed to the novel geometric-electronic effects of C<sub>60</sub>, acting as “hydrogen shuttle” and “electron sponge”, which illustrates the important role of carbon-based supports in single-atom catalysts. Our work not only unveils the basic structures and bonding nature of fullerene–metal clusters but also elucidates their potential importance in astrophysics, astrochemistry, and catalysis, showing the multifaceted character of this class of clusters. More exciting and interesting aspects of the fullerene–metal clusters, such as ultrafast charge-transfer dynamics between fullerene and metal and their relevance to designing hybrid fullerene–metal junctions for electronic devices, are awaiting exploration.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4000,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Multifacets of Fullerene–Metal Clusters: From Fundamental to Application\",\"authors\":\"Jianzhi Xu, Ya-Ke Li, Ewald Janssens and Gao-Lei Hou, \",\"doi\":\"10.1021/acs.accounts.4c00130\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Buckminsterfullerene, C<sub>60</sub>, was discovered through a prominent mass peak containing 60 atoms produced from laser vaporization of graphite, driven by Kroto’s interest in understanding the formation mechanisms of carbon-containing molecules in space. Inspired by the geodesic dome-shaped architecture designed by Richard Buckminster Fuller, after whom the particle was named, C<sub>60</sub> was found to have a football-shaped structure comprising 20 hexagons and 12 pentagons. It sparked worldwide interest in understanding this new carbon allotrope, resulting in the awarding of the Noble Prize in Chemistry to Smalley, Kroto, and Curl in 1996.</p><p >Intrinsically, C<sub>60</sub> is an exceptional species because of its high stability and electron-accepting ability and its structural tunability by decorating or substituting either on its exterior surface or interior hollow cavity. For example, metal-decorated fullerene complexes have found important applications ranging from superconductivity, nanoscale electronic devices, and organic photovoltaic cells to catalysis and biomedicine. Compared to the large body of studies on atoms and molecules encapsulated by C<sub>60</sub>, studies on the exteriorly modified fullerenes, i.e., exohedral fullerenes, are scarcer. Surprisingly, to date, uncertainty exists about a fundamental question: what is the preferable exterior binding site of different kinds of single atoms on the C<sub>60</sub> surface?</p><p >In recent years, we have developed an experimental protocol to synthesize the desired fullerene–metal clusters and to record their infrared spectra via messenger-tagged infrared multiple photon dissociation spectroscopy. With complementary quantum chemical calculations and molecular dynamics simulations, we determined that the most probable binding site of a metal, specifically a vanadium cation, on C<sub>60</sub> is above a pentagonal center in an η<sup>5</sup> fashion. We explored the bonding nature between C<sub>60</sub> and V<sup>+</sup> and revealed that the high thermal stability of this cluster originates from large orbital and electrostatic interactions. Through comparing the measured infrared spectra of [C<sub>60</sub>-Metal]<sup>+</sup> with the observational Spitzer data of several fullerene-rich planetary nebulae, we proposed that the complexes formed by fullerene and cosmically abundant metals, for example, iron, are promising carriers of astronomical unidentified spectroscopic features. This opens the door for a real consideration of Kroto’s 30-year-old hypothesis that complexes involving cosmically abundant elements and C<sub>60</sub> exhibit strong charge-transfer bands, similar to those of certain unidentified astrophysical spectroscopic features. We compiled a VibFullerene database and extracted a set of vibrational frequencies and intensities for fullerene derivatives to facilitate their potential detection by the James Webb Space Telescope. In addition, we showed that upon infrared irradiation C<sub>60</sub>V<sup>+</sup> can efficiently catalyze water splitting to generate H<sub>2</sub>. This finding is attributed to the novel geometric-electronic effects of C<sub>60</sub>, acting as “hydrogen shuttle” and “electron sponge”, which illustrates the important role of carbon-based supports in single-atom catalysts. Our work not only unveils the basic structures and bonding nature of fullerene–metal clusters but also elucidates their potential importance in astrophysics, astrochemistry, and catalysis, showing the multifaceted character of this class of clusters. More exciting and interesting aspects of the fullerene–metal clusters, such as ultrafast charge-transfer dynamics between fullerene and metal and their relevance to designing hybrid fullerene–metal junctions for electronic devices, are awaiting exploration.</p>\",\"PeriodicalId\":1,\"journal\":{\"name\":\"Accounts of Chemical Research\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.4000,\"publicationDate\":\"2024-04-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Accounts of Chemical Research\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.accounts.4c00130\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Accounts of Chemical Research","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.accounts.4c00130","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Multifacets of Fullerene–Metal Clusters: From Fundamental to Application
Buckminsterfullerene, C60, was discovered through a prominent mass peak containing 60 atoms produced from laser vaporization of graphite, driven by Kroto’s interest in understanding the formation mechanisms of carbon-containing molecules in space. Inspired by the geodesic dome-shaped architecture designed by Richard Buckminster Fuller, after whom the particle was named, C60 was found to have a football-shaped structure comprising 20 hexagons and 12 pentagons. It sparked worldwide interest in understanding this new carbon allotrope, resulting in the awarding of the Noble Prize in Chemistry to Smalley, Kroto, and Curl in 1996.
Intrinsically, C60 is an exceptional species because of its high stability and electron-accepting ability and its structural tunability by decorating or substituting either on its exterior surface or interior hollow cavity. For example, metal-decorated fullerene complexes have found important applications ranging from superconductivity, nanoscale electronic devices, and organic photovoltaic cells to catalysis and biomedicine. Compared to the large body of studies on atoms and molecules encapsulated by C60, studies on the exteriorly modified fullerenes, i.e., exohedral fullerenes, are scarcer. Surprisingly, to date, uncertainty exists about a fundamental question: what is the preferable exterior binding site of different kinds of single atoms on the C60 surface?
In recent years, we have developed an experimental protocol to synthesize the desired fullerene–metal clusters and to record their infrared spectra via messenger-tagged infrared multiple photon dissociation spectroscopy. With complementary quantum chemical calculations and molecular dynamics simulations, we determined that the most probable binding site of a metal, specifically a vanadium cation, on C60 is above a pentagonal center in an η5 fashion. We explored the bonding nature between C60 and V+ and revealed that the high thermal stability of this cluster originates from large orbital and electrostatic interactions. Through comparing the measured infrared spectra of [C60-Metal]+ with the observational Spitzer data of several fullerene-rich planetary nebulae, we proposed that the complexes formed by fullerene and cosmically abundant metals, for example, iron, are promising carriers of astronomical unidentified spectroscopic features. This opens the door for a real consideration of Kroto’s 30-year-old hypothesis that complexes involving cosmically abundant elements and C60 exhibit strong charge-transfer bands, similar to those of certain unidentified astrophysical spectroscopic features. We compiled a VibFullerene database and extracted a set of vibrational frequencies and intensities for fullerene derivatives to facilitate their potential detection by the James Webb Space Telescope. In addition, we showed that upon infrared irradiation C60V+ can efficiently catalyze water splitting to generate H2. This finding is attributed to the novel geometric-electronic effects of C60, acting as “hydrogen shuttle” and “electron sponge”, which illustrates the important role of carbon-based supports in single-atom catalysts. Our work not only unveils the basic structures and bonding nature of fullerene–metal clusters but also elucidates their potential importance in astrophysics, astrochemistry, and catalysis, showing the multifaceted character of this class of clusters. More exciting and interesting aspects of the fullerene–metal clusters, such as ultrafast charge-transfer dynamics between fullerene and metal and their relevance to designing hybrid fullerene–metal junctions for electronic devices, are awaiting exploration.
期刊介绍:
Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance.
Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.